Incineration Techniques for Control of Volatile Organic Compound Emissions

A review of incineration techniques for control of volatile organic compound emissions is presented in two consecutive issues o/JAPCA. Part I presented an overview of the process including fundamentals and design considerations. Both thermal and catalytic incinerators were considered. Part IIpresents capital and annual operating cost estimates for both thermal and catalytic incinerator systems based on information received from a number of equipment manufacturers.     

Source Location and Characterization of Volatile Organic Compound Emissions at a Petrochemical Plant in Kaohsiung,Taiwan

Abstract

This paper elucidated a novel approach to locating volatile organic compound (VOC) emission sources and characterizing their VOCs by database and contour plotting. The target of this survey was a petrochemical plant in Linyan, Kaohsiung County, Taiwan. Samples were taken with canisters from 25 sites inside this plant, twice per season, and analyzed by gas chromatography–mass spectrometry. The survey covered 1 whole year. By consolidated into a database, the data could be readily retrieved, statistically analyzed, and clearly presented in both table and graph forms. It followed from the cross‐analysis of the database that the abundant types of VOCs were alkanes, alkenes/dienes, and aromatics, all of which accounted for 99% of total VOCs. By contour plotting, the emission sources for alkanes, aromatics, and alkenes/dienes were successfully located. Through statistical analysis, the database could provide the range and 90% confidence interval of each species from each emission source. Both alkanes and alkene/dienes came from tank farm and naphtha cracking units and were mainly composed of C₃–C₅ members. Regarding aromatics, benzene, toluene, and xylenes were the primary species; they were emitted from tank farm, aromatic units, and xylene units.     

Incineration Techniques for Control of Volatile Organic Compound Emissions Part I. Fundamentals and Process Design Considerations

A review of incineration techniques for control of volatile organic compound emissions is presented in two consecutive issues of JAPC A. Part I presents an overview of the process including fundamentals and design considerations. Both thermal and catalytic incincerators are considered. Part II will present capital and annual operating cost estimates for both thermal and catalytic incinerator systems based on information received from a number of equipment manufacturers.     

Wet Scrubber Analysis of Volatile Organic Compound Removal in the Rendering Industry

Abstract

The promulgation of odor control rules, increasing public concerns, and U.S. Environmental Protection Agency (EPA) air regulations in nonattainment zones necessitates the remediation of a wide range of volatile organic compounds (VOCs) generated by the rendering industry. Currently, wet scrubbers with oxidizing chemicals are used to treat VOCs; however, little information is available on scrubber efficiency for many of the VOCs generated within the rendering process. Portable gas chromatography/mass spectrometry (GC/MS) units were used to rapidly identify key VOCs on-site in process streams at two poultry byproduct rendering plants. On-site analysis was found to be important, given the significant reduction in peak areas if samples were held for 24 hr before analysis. Major compounds consistently identified in the emissions from the plant included dimethyl disulfide, methanethiol, octane, hexanal, 2-methylbutanal, and 3-methylbutanal. The two branched aldehydes, 2-methylbutanal and 3-methylbutanal, were by far the most consistent, appearing in every sample and typically the largest fraction of the VOC mixture.

A chlorinated hydrocarbon, methanesulfonyl chloride, was identified in the outlet of a high-intensity wet scrubber, and several VOCs and chlorinated compounds were identified in the scrubbing solution, but not on a consistent basis. Total VOC concentrations in noncondensable gas streams ranged from 4 to 91 ppmv. At the two plants, the odor-causing compound methanethiol ranged from 25 to 33% and 9.6% of the total VOCs (v/v). In one plant, wet scrubber analysis using chlorine dioxide (ClO2) as the oxidizing agent indicated that close to 100% of the methanethiol was removed from the gas phase, but removal efficiencies ranged from 20 to 80% for the aldehydes and hydrocarbons and from 23 to 64% for total VOCs. In the second plant, conversion efficiencies were much lower in a packed-bed wet scrubber, with a measurable removal of only dimethyl sulfide (20–100%).     

Estimation of Organic Compound Emissions from Waste Lagoons

Abstract

With the recent focus on fine particle matter (PM_2.5),new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference.The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO₂, nitrogen oxide, volatile organic compound, and NH₃ is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM_2.5 mass emission rates in the range of ～10_-4 lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with ～5 × 10_-3 lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of ～0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM_2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM_2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or woodfueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing “true” particulate carbon emission results.     

Variations in the Emissions of Volatile Organic Compounds from the Toner for a Specific Photocopier

ABSTRACT

A laboratory thermal desorption apparatus was used to measure emissions from a number of nominally identical photocopier toners—manufactured to meet the specifications of one specific model copier—when these toners were heated to fuser temperature (180-200 °C). The objective was to assess how potential volatile organic compound (VOC) emissions from the toner for a given copier can vary, depending upon the production run and the supplier. Tests were performed on a series of toner (and associated raw polymer feedstock) samples obtained directly from a toner manufacturer, representing two production runs using a nonvented extrusion process, and on toner cartridges purchased from two local retailers, representing three different production lots (histories unknown). The results showed that the retailer toners consistently had up to 350% higher emissions of some major compounds (expressed as |ig of compound emit-ted/g of toner), and up to 100% lower emissions of others, relative to the manufacturer toners (p ≤ 0.01). The manufacturer toners from one production run had emissions of certain compounds, and of total VOCs, that were modestly higher (13-18%) than those from the other run (p ≤ 0.01). The emission differences between the retailer and manufacturer toners are probably due to differences     

Characterization of Emissions of Volatile Organic Compounds from Interior Alkyd Paint

ABSTRACT

Alkyd paint continues to be used indoors for application to wood trim, cabinet surfaces, and some kitchen and bathroom walls. Alkyd paint may represent a significant source of volatile organic compounds (VOCs) indoors because of the frequency of use and amount of surface painted. The U.S. Environmental Protection Agency (EPA) is conducting research to characterize VOC emissions from paint and to develop source emission models that can be used for exposure assessment and risk management. The technical approach for this research involves both analysis of the liquid paint to identify and quantify the VOC contents and dynamic small chamber emissions tests to characterize the VOC emissions after application. The predominant constituents of the primer and two alkyd paints selected for testing were straight-chain alkanes (C9–C12); C8–C9 aromatics were minor constituents. Branched chain alkanes were the predominant VOCs in a third paint. A series of tests were performed to evaluate factors that may affect emissions following application of the coatings. The type of substrate (glass, wallboard, or pine board) did not have a substantial impact on the emissions with respect to peak concentrations, the emissions profile, or the amount of VOC mass emitted from the paint. Peak concentrations of total volatile organic compounds (TVOCs) as high as 10,000 mg/m³ were measured during small chamber emissions tests at 0.5 air exchanges per hour (ACH). Over 90% of the VOCs were emitted from the primer and paints during the first 10 hr following application. Emissions were similar from paint applied to bare pine board, a primed board, or a board previously painted with the same paint. The impact of other variables, including film thickness, air velocity at the surface, and air-exchange rate (AER) were consistent with theoretical predictions for gas-phase, mass transfer-controlled emissions. In addition to the alkanes and aromatics, aldehydes were detected in the emissions during paint drying. Hexanal, the predominant aldehyde in the emissions, was not detected in the liquid paint and was apparently an oxidation product formed during drying. This paper summarizes the results of the product analyses and a series of small chamber emissions tests. It also describes the use of a mass balance approach to evaluate the impact of test variables and to assess the quality of the emissions data.     

Performance of a Pilot-Scale Biotrickling Filter in Controlling the Volatile Organic Compound Emissions in a Furniture Manufacturing Facility

Abstract

A 0.75-m³ pilot-scale biotrickling filter was run for over 1 yr in a Spanish furniture company to evaluate its performance in the removal of volatile organic compounds (VOCs) contained in the emission of two different paint spray booths. The first one was an open front booth used to manually paint furniture, and the second focus was an automatically operated closed booth operated to paint pieces of furniture. In both cases, the VOC emissions were very irregular, with rapid and extreme fluctuations. The pilot plant was operated at an empty bed residence time (EBRT) ranging from 10 to 40 sec, and good removal efficiencies of VOCs were usually obtained. When a buffering activated carbon prefllter was installed, the system performance was improved considerably, so a much better compliance with legal constraints was reached. After different shutdowns in the factory, the period to recover the previous performance of the biotrickling reactor was minimal. A weekend dehydration strategy was developed and implemented to control the pressure drop associated with excessive biomass accumulation.     

Biofilter Treatment of Volatile Organic Compound Emissions from Reformulated Paint: Complex Mixtures,Intermittent Operation,and Startup

Abstract

Two biofilters were operated to treat a waste gas stream intended to simulate off-gases generated during the manufacture of reformulated paint. The model waste gas stream consisted of a five-component solvent mixture containing acetone (450 ppm_v), methyl ethyl ketone (12 ppm_v), toluene (29 ppm_v), ethylbenzene (10 ppm_v), and p-xylene (10 ppm_v). The two biofilters, identical in construction and packed with a polyurethane foam support medium, were inoculated with an enrichment culture derived from compost and then subjected to different loading conditions during the startup phase of operation. One biofilter was subjected to intermittent loading conditions with contaminants supplied only 8 hr/day to simulate loading conditions expected at facilities where manufacturing operations are discontinuous. The other biofilter was subjected to continuous contaminant loading during the initial start period, and then was switched to intermittent loading conditions. Experimental results demonstrate that both startup strategies can ultimately achieve high contaminant removal efficiency (>99%) at a target contaminant mass loading rate of 80.3 g m^?3 hr^?1 and an empty bed residence time of 59 sec. The biofilter subjected to intermittent loading conditions at startup, however, took considerably longer to reach high performance. In both biofilters, ketone components (acetone and methyl ethyl ketone) were more rapidly degraded than aromatic hydrocarbons (toluene, ethylbenzene, and p-xylene). Scanning electron microscopy and plate count data revealed that fungi, as well as bacteria, populated the biofilters.     

Control of Organic Emissions from Surface Coating Operations

ABSTRACT

Step tracer tests were carried out on lab-scale biofilters to determine the residence time distributions (RTDs) of gases passing through two types of biofilters: a standard biofilter with vertical gas flow and a modified biofilter with horizontal gas flow. Results were used to define the flow patterns in the reactors. “Non-ideal flow” indicates that the flow reactors did not behave like either type of ideal reactor: the perfectly stirred reactor [often called a "continuously stirred tank reactor" (CSTR)] or the plug-flow reactor.

The horizontal biofilter with back-mixing was able to accommodate a shorter residence time without the usual requirement of greater biofilter surface area for increased biofiltration efficiency. Experimental results indicated that the first bed of the modified biofilter behaved like two CSTRs in series, while the second bed may be represented by two or three CSTRs in series. Because of the flow baffles used in the horizontal biofilter system, its performance was more similar to completely mixed systems, and hence, it could not be modeled as a plug-flow reactor. For the standard biofilter, the number of CSTRs was found to be between 2 and 9 depending on the airflow rate. In terms of NH₃ removal efficiency and elimination capacity, the standard biofilter was not as good as the modified system; moreover, the second bed of the modified biofilter exhibited greater removal efficiency than the first bed. The elimination rate increased as biofilter load increased. An opposite trend was exhibited with respect to removal efficiency.     

Near Surface Soil Vapor Clusters for Monitoring Emissions of Volatile Organic Compounds from Soils

ABSTRACT

The overall objective of this research was to develop and test a method of determining emission rates of volatile organic compounds (VOCs) and other gases from soil surfaces. Soil vapor clusters (SVCs) were designed as a low dead volume, robust sampling system to obtain vertically resolved profiles of soil gas contaminant concentrations in the near surface zone. The concentration profiles, when combined with a mathematical model of porous media mass transport, were used to calculate the contaminant flux from the soil surface. Initial experiments were conducted using a mesoscale soil remediation system under a range of experimental conditions. Helium was used as a tracer and trichloroethene was used as a model VOC. Flux estimations using the SVCs were within 25% of independent surface flux estimates and were comparable to measurements made using a surface isolation flux chamber (SIFC). In addition, method detection limits for the SVC were an order of magnitude lower than detection limits with the SIFC. Field trials, conducted with the SVCs at a bioventing site, indicated that the SVC method could be easily used in the field to estimate fugitive VOC emission rates. Major advantages of the SVC method were its low detection limits, lack of required auxiliary equipment, and ability to obtain realtime estimates of fugitive VOC emission rates.     

Evaluation of Canisters for Measuring Emissions of Volatile Organic Air Pollutants from Hazardous Waste Incineration

Regulation to control air emissions of toxic organic compounds require the collection and analysis of effluent gas from low level sources such as hazardous waste incinerators. The standard SW- 846 Method specifies the use of Tenax and Tenax/charcoal adsorbent traps for collection of volatile organics from incinerators. This study evaluates passivated stainless steel canisters as an alternative to adsorbent traps to eliminate some of the problems associated with adsorbent sampling. Initially the stability of 18 nonpolar, volatile organic compounds was determined in Summa-treated stainless steel canisters with greater than 100 ppmv HCI and saturated with water vapor. All 18 components were stable for a twoweek period; however, an Interference caused a 10-fold increase In the FID response of trlchloroethylene, toluene, and chlorobenzene. No Interference of the ECD response was found for any of the 11 compounds detected with the ECD including trlchloroethylene. A pilot scale incinerator was sampled using canisters, and the destruction efficiency of 1,1,1-trichloroethane was determined at a concentration of less than 0.5 ppbv while determining 1,1-dichloroethylene, the major product of Incomplete combustion, at a concentration of 8000 ppbv from the same sample.     

Ozone Control Strategies Based on the Ratio of Volatile Organic Compounds to Nitrogen Oxides

The 1990 Clean Air Act Amendments require states with O₃ nonattainment areas to adopt regulations to enforce reasonable available control technologies (RACT) for NO_X stationary sources by November 1992. However, if the states can demonstrate that such measures will have an adverse effect on air quality, NO_X requirements may be waived. To assist the states in making this decision, the U.S. EPA is attempting to develop guidelines for the states to use in deciding whether NO_X reductions will have a positive or negative impact on O3 air quality. Although NO_X is a precursor of O₃, at low VOC/NO_X ratios, the reduction of NO_X can result in increased peak O₃. EPA is examining existing information on VOC/NO_X ratios to develop “rules of thumb” to guide the states in their decision-making process. An examination of 6 a.m. to 9 a.m. VOC/NO_X ratios at a number of sites in the eastern U.S. indicates that the ratio is highly variable from day-to-day and there is no apparent relationship between ratios measured at different sites within the same area. In addition, statistical analysis failed to identify significant relationships between the 6 a.m. to 9 a.m. VOC/NO_X ratio and the maximum 1-hr. O₃ within a given area. Since we know from smog chamber and modeling studies that such a relationship exists, this further invalidates the assumption that a ratio measured at a single site is representative of the ratio for the entire region. Based on this Information, we conclude that having the 6 a.m. to 9 a.m. ambient VOC/NO_X ratio for a given area is insufficient information, by itself, to decide whether a VOC-alone, a NO_x-alone, or a combined VOC-NO_X reduction strategy is a viable or optimum O₃-reduction strategy.     

Alternative Strategies for Control of Sulfur Dioxide Emissions

Achievement of air quality goals now more than ever requires careful consideration of alternative control strategies in view of national concerns with energy and the economy. Three strategies which might be used by coal-fired steam electric plants to achieve ambient air quality standards for sulfur dioxide have been compared, and the analysis shows that the desired objective can be achieved using the intermittent control strategy with substantially less impact on the environment, less consumption of energy, and at a much lower economic cost than using either stack gas scrubbing or low-sulfur coal.     

Economic Study of the Tunable Electron Beam Plasma Reactor for Volatile Organic Compound Treatment

ABSTRACT

A tunable electron beam generated plasma system has been developed for selective cold plasma treatment of dilute concentrations (1-3,000 ppm range) of hazardous compounds in gaseous waste treatment. This system, referred to as the Tunable Hybrid Plasma (THP), has shown a high degree of efficiency and effectiveness in both laboratory and field tests. Decomposition energy requirements are in the 100 eV per molecule range for treatment of carbon tetrachloride and 10 eV for treatment of trichloroethylene.

A cost comparison has been made between the Tunable Hybrid Plasma (THP) technology and three conventional technologies used for emission control of volatile organic compounds (VOCs): granular activated carbon, thermal incineration, and catalytic oxidation. In addition to its environmentally attractive features, THP technology has the potential to be lower cost than other technologies over a range of concentrations and flow rates. Cost projections for the THP system for decomposition of trichloroet-hylene are around 50 cents/lb for initial concentrations in the few hundred ppm range and flow rates of 5,000 cfm or greater and around $1/lb for 1,000 cfm flow rates. Cost projections for carbon tetrachloride and trichloroethane decomposition using the THP technology are several dollars per pound. The costs for THP treatment are generally significantly lower than costs for use of granular activated carbon and are also quite competitive with costs for thermal incineration and catalytic oxidation.     

Measuring the Organic Carbon Content of Source Emissions for Air Pollution Control

Measuring emissions of organic materials from such sources as paint bake ovens, degreas-ing operations, and printing processes is a necessy part of a control program for solvents. Over the intervening years since 1966 when Los Angeles first enacted its solvent Rule 66, a considerable number of tests have been performed and the present test method has gone through a period of experience and improvement. A sample is collected from a stack or vent in a freeze-out trap cooled with dry ice followed by an evacuated 8-liter tank. Analysis is done by a system of gas chromatography and catalytic combustion to yield the total organic carbon content. Representative industrial emission analysis results, which demonstrate the practical applicability of the system, are shown.     

Determination of Source Contributions to Ambient Volatile Organic Compound Concentrations in Berlin

ABSTRACT

During three measuring campaigns in June, July, and August 1996, volatile organic compound (VOC) concentrations were measured at a rural background site, a city residential site, and a street site in Berlin. In addition, samples were taken near relevant sources of VOCs. The meaurements covered the volatile hydrocarbons in the range C₁-C₁₄ and included aldehydes and ketones. Samples were taken at four characteristic periods of 2 hr/day: during the night, during the early morning rush hour, at midday, and during the evening rush hour. An assessment of the contribution of emission categories to the observed concentrations was made with the chemical mass balance (CMB) modelling technique.

The VOC concentrations at the residential area and at the street site in the inner city were, respectively, a factor of 3 and 7 above the background concentration. Traffic exhaust contributed approximately 80-90% of the non-methane hydrocarbon (NMHC) concentration in the inner city and approximately 60% at the background area. Evaporative losses of motor fuel are estimated to account for approximately 7% at all sites. Natural gas leakage also contributed significantly to the observed VOC concentrations: in the inner city approximately 510% and at the background area approximately 30%. The measurements also showed a contribution of smaller sources, such as dry cleaning, use of solvents, and bio-genic emissions. However, the contribution of these sources to the total observed concentrations at the sites is estimated to be very small.     

Investigation to Determine the Possible Need for a Regulation on Organic Compound Emissions from Stationary Sources in the San Francisco Bay Area

The problem of an investigation of the need for a regulation on organic compound emissions in the San Francisco Bay Area can be divided into two major areas: 1. Is there a need for a regulation on organic compound emissions? What is the extent of photochemical smog effects? How much control is necessary to achieve the desired effects?

2. (2) If the need exists for an organic compound regulation, can a performance type regulation be written for all types of organic compound emissions? Must the regulation be directed toward specific industries or types of emissions? Can the regulation be adequately enforced—both practically and legally?

This paper will describe the studies undertaken by the District Staff to answer the first set of questions. Work covering the second group of questions is now under investigation.     

Fugitive Dust Emission Source Profiles and Assessment of Selected Control Strategies for Particulate Matter at Gravel Processing Sites in Taiwan

Abstract

Particles emitted from gravel processing sites are one contributor to worsening air quality in Taiwan. Major pollution sources at gravel processing sites include gravel and sand piles, unpaved roads, material crushers, and bare ground. This study analyzed fugitive dust emission characteristics at each pollution source using several types of particle samplers, including total suspended particulates (TSP), suspended particulate (PM₁₀), fine suspended particulate (PM_2.5), particulate sizer, and dust-fall collectors. Furthermore, silt content and moisture in the gravel were measured to develop particulate emission factors. The results showed that TSP (<100 µm) concentrations at the boundary of gravel sites ranged from 280 to 1290 µg/m³, which clearly exceeds the Taiwan hourly air quality standard of 500 µg/m³. Moreover, PM₁₀ concentrations, ranging from 135 to 550 µg/m³, were also above the daily air quality standard of 125 µg/m³ and approximately 1.2 and 1.5 times the PM_2.5 concentrations, ranging from 105 to 470 µg/m³. The size distribution analysis reveals that mass mean diameter and geometric standard deviation ranged from 3.2 to 5.7 µm and from 2.82 to 5.51, respectively. In this study, spraying surfactant was the most effective control strategy to abate windblown dust from unpaved roads, having a control efficiency of approximately 93%, which is significantly higher than using paved road strategies with a control efficiency of approximately 45%. For paved roads, wet suppression provided the best dust control efficiencies ranging from 50 to 83%. Re-vegetation of disturbed ground had dust control efficiencies ranging from 48 to 64%.     

Inter-Urban Comparison of Ambient Volatile Organic Compound Concentrations in U.S. Cities

Airborne particulate matter from three ferrous foundries was sampled in granulometric fractions and analyzed by scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDXA), X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) to determine morphology and qualitative bulk and surface chemical compositions. Cluster and principal components analyses (PCA) were used as an aid for interpretation of results. A clear pattern of composition as a function of size emerges; in particular, trace metals accumulate in fine particles and volatile species on the surface of these. Chemical composition changes are also related to daily schedules where applicable: trace metals appear during pouring operations, silicon is generated during mold making and unmolding. Cluster and PCA greatly ease examination of data and offer pictorial representations of results; in particular, the chemical composition versus particle size relationship is very neatly illustrated by PCA graphs.